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| United States Patent |
6,146,497
|
|
Nguyen
|
November 14, 2000
|
Adhesives and resins, and processes for their production
Abstract
Additives for addition to starting materials in cellulose based products
for imparting strength and crepe. Additives for use in paper production
which impart strength to the product and which can be used in creping
adhesives. Enzyme activated resins for use in paper production.
Enzyme-activated adhesives for use in paper production. Paper products
comprising the aforementioned additives or resins. Methods for imparting
strength or crepe to paper products.
| Inventors:
|
Nguyen; Tuyen T. (Wilmington, DE)
|
| Assignee:
|
Hercules Incorporated (Wilmington, DE)
|
| Appl. No.:
|
008079 |
| Filed:
|
January 16, 1998 |
| Current U.S. Class: |
162/158; 162/164.1; 162/165; 162/166; 162/183; 524/547; 524/555; 524/557; 524/560; 524/565; 525/328.5; 525/329.4; 525/330.6 |
| Intern'l Class: |
D21F 011/00; D21H 023/00 |
| Field of Search: |
525/328.8,328.5,61,329.4,330.6,329.1
524/557,547,555,560,565
528/211,228,229
162/158,168,165,164.1,183
|
References Cited
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| 5846788 | Dec., 1998 | Pedersen et al. | 435/101.
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| |
Other References
Akkara et al., "Synthesis and Charaxterization of Polyphenols from
Peroxidase-Catalyzed Reactions," Enzyme Microb. Technol. vol. 13, p. 521
(Jun. 1991).
Bruno et al., "Enzyme Catalyzed 2-D Polymerization of Phenol Derivatives on
a Langmuir-Blodgett Trough," Polymer Reprints, vol. 32, No. 1, pp. 232-233
(1991).
Casey, Pulp and Paper, vol. 1, pp. 159-162. Publication Date is not
Disclosed.
Schmalz, TAPPI 44, No. 4, pp. 275-280 (Apr. 1961).
Sperling and Mishra, in "Polymers for Advanced Technologies, vol. 7" ppl.
197-208, 1996.
TAPPI Method T 205PM-88 (1988).
Casey, Pulp and Paper, vol. I, p. 341. Publication Date is not Disclosed.
Dordick et al., "Polymerization of Phenols Catalyzed by Peroxidase in
Nonaqueous Media," Biotechnology and Bioengineering, vol. 30, pp. 31-36
(1987).
Espy, "The Mechanism of Wet-Strength Development in Paper: A Review," Tappi
Journal, vol. 78, No. 4, pp. 90-97 (Apr. 1995).
Westfelt, "Chemistry of Paper Wet-Strength. I. A Survey of Mechanism of
Wet-Strength Development," Cellulose Chemistry and Technology, vol. 13,
pp. 813-825 (1979).
|
Primary Examiner: Seidleck; James J.
Assistant Examiner: Rajguru; U. K.
Attorney, Agent or Firm: Greenblum & Bernstein, P.L.C.
Claims
What is claimed is:
1. A composition comprising (a) water-soluble polymeric material comprising
at least one nucleophilic polymer, (b) phenolic compound, and (c) a
component capable of converting the phenolic compound into a quinone
compound.
2. A composition comprising (a) water-soluble polymeric material comprising
at least one nucleophilic polymer, (b) phenolic compound, and (c) an
oxidizing component.
3. The composition of claim 2, wherein the oxidizing component comprises a
member selected from the group consisting of potassium dichromate,
potassium permanganate, and mixtures thereof.
4. The composition of claim 2, wherein the oxidizing component comprises a
metal catalyst and hydrogen peroxide.
5. The composition of claim 4, wherein the metal catalyst is selected from
the group consisting of ferric chloride, cupric chloride, cobalt chloride,
and mixtures thereof.
6. The composition of claim 2, wherein the oxidizing component comprises an
enzyme system.
7. The composition of claim 6, wherein the at least one nucleophilic
polymer comprises the following general structure:
##STR8##
wherein n is an integer greater than 2, and R.sup.1 comprises a
hydrocarbyl group comprising from about 2 to about 20 carbons.
8. The composition of claim 7, wherein the hydrocarbyl group comprises an
alkyl group.
9. The composition of claim 8, wherein the alkyl group comprises from about
6 to about 10 carbons.
10. The composition of claim 9, wherein the alkyl group comprises about 6
carbons.
11. The composition of claim 7, wherein n is from about 10 to about 200.
12. The composition of claim 11, wherein n is from about 50 to about 100.
13. The composition of claim 12, wherein n is from about 50 to about 80.
14. The composition of claim 9, wherein the at least one nucleophilic
polymer comprises a member selected from the group consisting of polyalkyl
amine, polycyclic alkyl amine, and mixtures thereof.
15. The composition of claim 6, wherein the at least one nucleophilic
polymer comprises the following general structure:
##STR9##
wherein n is an integer greater than 2, X comprises a nucleophile, and Y
comprises a water solubility enabling group.
16. The composition of claim 15, wherein the nucleophile comprises a member
selected from the group consisting of --NH.sub.2, --NHR.sup.2, --SH,
--SOO.sup.-, --ArO.sup.-, and --PR.sup.2.sub.2, wherein R.sup.2 comprises
a hydrocarbyl group comprising from about 1 to about 12 carbons, and Ar
comprises a benzenoid, a substituted benzenoid, or a napthalenoid group.
17. The composition of claim 16, wherein the hydrocarbyl group comprises a
benzenoid group or an alkyl group.
18. The composition of claim 15, wherein the water solubility enabling
group comprises a member selected from the group consisting of cationic,
anionic, amphoteric, hydrogen bond participating groups, and mixtures
thereof.
19. The composition of claim 15, wherein the water solubility enabling
group comprises a member selected from the group consisting of --N.sup.+
(R.sup.3).sub.3, --COO.sup.-, --OSO.sub.3.sup.-, --OPO.sub.3.sup.-,
--N.sup.+ (R.sup.3).sub.2 --R.sup.3' --COO.sup.-, --OH, --CONH.sub.2,
--B(OH).sub.2, and mixtures thereof, wherein R.sup.3 and R.sup.3'
comprise any moiety having from about 1 to about 12 carbons.
20. The composition of claim 6, wherein the at least one nucleophilic
polymer comprises a member selected from the group consisting of polyvinyl
alcohols, polyvinyl sulfones, polyacrylamides, polyacrylates,
polyacrylonitriles, polyethers, polyesters, polyarylethers,
polyarylsulfones, polyamides, polyimides, polyalkanes, polyaminoalkanes,
polyphenyls, and mixtures thereof.
21. The composition of claim 6, wherein the at least one nucleophilic
polymer is formed by a process comprising at least one addition reaction
followed by reduction.
22. The composition of claim 6, wherein the at least one nucleophilic
polymer comprises a member selected from the group consisting of
--NH.sub.2, --NHR.sup.4, --SH, --SOO.sup.-, --PR.sup.4.sub.2, --ArO.sup.-,
and mixtures thereof, wherein R.sup.4 comprises a hydrocarbyl group
comprising between about 1 and about 12 carbons, and Ar comprises a
benzenoid or a napthalenoid group.
23. The composition of claim 22, wherein the hydrocarbyl group comprises a
benzenoid group or an alkyl group.
24. The composition of claim 6, wherein the at least one nucleophilic
polymer is formed by polymerizing a monomer comprising a nucleophile.
25. The composition of claim 6, wherein the at least one nucleophilic
polymer comprises polyvinyl amine alcohol.
26. The composition of claim 25, wherein the polyvinyl amine alcohol
comprises from about 0.01% to about 100% amine.
27. The composition of claim 26, wherein the polyvinyl amine alcohol
comprises from about 10% to about 50% amine.
28. The composition of claim 27, wherein the polyvinyl amine alcohol
comprises about 12% amine.
29. The composition of claim 6, wherein the phenolic compound comprises a
polyphenolic compound.
30. The composition of claim 29, wherein the polyphenolic compound
comprises a member selected from the group consisting of phloroglucinol,
lignins, catechins, flavonoids, and mixtures thereof.
31. The composition of claim 29, wherein the polyphenolic compound
comprises a member selected from the group consisting of polyphenols,
resols, novolaks, calixerenes, and mixtures thereof.
32. The composition of claim 6, wherein the phenolic compound comprises the
following general chemical structure:
##STR10##
wherein Y comprises --H or --OH and X comprises --OR.sup.5, --R.sup.5,
--Ar, or --NR.sup.5 R.sup.5', wherein R.sup.5 and R.sup.5' comprise H or
a hydrocarbyl group comprising from about 1 to about 12 carbons, and Ar
comprises a benzenoid or napthalenoid group.
33. The composition of claim 32, wherein the hydrocarbyl group comprises an
alkyl group.
34. The composition of claim 6, wherein the phenolic compound comprises a
member selected from the group consisting of polyphenols, substituted
polyphenols, phenols, substituted phenols, catechols, substituted
catechols, hydroquinones, substituted hydroquinones, aminophenols,
substituted aminophenols, and mixtures thereof.
35. The composition of claim 34, wherein the phenolic material comprises
1,2-benzenediol.
36. The composition of claim 34, wherein the phenolic material comprises
1,4-benzenediol.
37. The composition of claim 6, wherein the enzyme system comprises at
least one oxidation enzyme.
38. The composition of claim 37, wherein the at least one oxidation enzyme
comprises an oxidase.
39. The composition of claim 37, wherein the at least one oxidation enzyme
comprises a peroxidase.
40. The composition of claim 39, wherein the peroxidase comprises a member
selected from the group consisting of horseradish peroxidases, soybean
peroxidases, haloperoxidases, lactoperoxidases, bacterial peroxidases, and
mixtures thereof.
41. The composition of claim 38, wherein the oxidase comprises a member
selected from the group consisting of laccase, tyrosinase, polyphenol
oxidase, and mixtures thereof.
42. The composition of claim 39, wherein the peroxidase comprises
horseradish peroxidase.
43. The composition of claim 6, wherein the enzyme system comprises at
least one oxygen source.
44. The composition of claim 43, wherein the oxygen source comprises a
member selected from the group consisting of perborates, persulfates,
peroxides, and mixtures thereof.
45. The composition of claim 6, wherein the enzyme system comprises an
alcohol oxidase and its corresponding alcohol.
46. The composition of claim 45, wherein the enzyme system comprises
ethanol and ethanol oxidase.
47. The composition of claim 6, wherein the enzyme system comprises a sugar
oxidase and its corresponding sugar.
48. The composition of claim 47, wherein the enzyme system comprises
glucose and glucose oxidase or galactose and galactose oxidase.
49. The composition of claim 6, in combination with a cellulosic material.
50. The composition of claim 49, wherein the cellulosic material comprises
paper pulp.
51. A resin for imparting strength to a paper product, produced by
combining (a) water-soluble polymeric material comprising at least one
nucleophilic polymer, (b) phenolic compound, and (c) an oxidizing
component.
52. The resin of claim 51, wherein the oxidizing component comprises an
enzyme system.
53. The resin of claim 51, in combination with cellulosic material.
54. The resin of claim 51, wherein the cellulosic material comprises a
member selected from the group consisting of fiber mat, woven cloth, box,
board, sheet, wood, particle board, wood stranded board, and laminate.
55. A creping adhesive, produced by combining (a) water-soluble polymeric
material comprising at least one nucleophilic polymer, (b) phenolic
compound, and (c) an oxidizing component.
56. The creping adhesive of claim 55, wherein the oxidizing component
comprises an enzyme system.
57. The creping adhesive of claim 55, in combination with cellulosic
material.
58. The creping adhesive of claim 57, wherein the cellulosic material
comprises a member selected from the group consisting of fiber mat, woven
cloth, box, board, sheet, wood, particle board, wood stranded board, and
laminate.
59. A method of increasing the strength of a paper product, comprising
adding (a) water-soluble polymeric material comprising at least one
nucleophilic polymer, (b) phenolic compound, and (c) an oxidizing
component, to paper pulp.
60. The method of claim 59, wherein the oxidizing component comprises an
enzyme system.
61. A method of imparting strength to a cellulose-based product comprising
adding (a) water-soluble polymeric material comprising at least one
nucleophilic polymer, (b) phenolic compound, and (c) an oxidizing
component, to cellulosic starting materials.
62. The method of claim 61, wherein the oxidizing component comprises an
enzyme system.
63. A resin for imparting strength to a paper product comprising the
composition of claim 2.
64. The resin of claim 63, wherein the oxidizing component comprises an
enzyme system.
65. A creping adhesive comprising the composition of claim 2.
66. The creping adhesive of claim 65, wherein the oxidizing component
comprises an enzyme system.
67. A kit comprising water-soluble polymeric material comprising (a) at
least one nucleophilic polymer, (b) phenolic compound, and (c) a component
capable of converting the phenolic compound into a quinone compound.
68. A composition comprising a polyvinyl alkylamine, a benzenediol, and
horseradish peroxidase.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to adhesives and resins, and processes for their
preparation. More particularly, this invention relates to resin and
adhesive compositions which can be particularly used in the manufacture of
cellulose-based products, and more particularly paper products. Resins and
adhesives of the present invention are produced by combining a
water-soluble polymeric material which comprises a nucleophile, a phenolic
material, and a component that serves to activate the phenolic material to
make it reactive with the nucleophile of the polymer. Adhesives and resins
produced according to the present invention are particularly useful in the
paper making industry but their application is not limited thereto.
2. Background of the Invention and Related Information
Many compositions for resins and adhesives are known in the art. Most of
these compositions, however, include components which can be considered
environmentally "unfriendly," or even toxic. In addition, some existing
adhesives and resins are, in themselves, environmentally "unfriendly" or
toxic. There is, therefore, a need for resins and adhesives which are
non-toxic and which are produced from non-toxic components.
The paper-making industry has long been concerned with ways of increasing
the strength of wetted paper. Paper constructed without additional means
of reinforcement will often fall apart upon rewetting. Paper which
maintains its strength upon wetting is desirable in many applications,
including bathroom tissue, paper towels, napkins, and the like. In
addition, additives which increase the strength of wet paper often
increase the dry strength of the same paper.
Many of the additives known in the art which can be used to increase the
wet strength of paper take advantage of the chemical structure of the
cellulose found therein. The cellulose found in paper products often has
carboxylate and hydroxyl moieties exposed along its chain. Through the use
of reactive additives, crosslinks can be formed between these moieties in
the chains of cellulose in the paper, thereby increasing the strength of
the paper. Alternatively, some additives do not react with the cellulose,
but increase the paper strength by some other, unknown mechanism. In
either case, the additives are usually chosen for their ability to adhere
to the pulp, and for their ability to form a structural network which can
repress cellulose fiber swelling, thereby inhibiting separation of the
fiber-fiber contacts upon wetting.
Some of the earliest wet-strength resins were condensation products of urea
and formaldehyde, with polyamine added to make the resin cationic. Such
resins appear only to impart wet-strength via self-crosslinking. However,
resins formed from melamine and formaldehyde appear to crosslink the
cellulose directly. Polyamide and epichlorohydrin form resins which react
with the cellulose carboxylate groups. At higher concentrations,
polyamide/epichlorohydrin resins appear to form self-crosslinks as well.
Other resins include those formed by epoxides, which react analogously and
also with the cellulose hydroxyl groups, and those formed from aldehydes,
which appear to crosslink cellulose reversibly, through hemiacetal bonds,
and self-crosslink at amide groups. A discussion of wet-strength resins
and their mechanisms is presented in "The Mechanism of Wet-Strength
Development in Paper: A Review," by Herbert H. ESPY, Tappi Journal, Vol.
78, No. 4, pages 90-97 (April 1995) as well as in "Chemistry of Paper
Wet-Strength. I. A Survey of Mechanisms of Wet-Strength Development," by
Lars WESTFELT, Cellulose Chemistry and Technology, Vol. 13, pages 813-825
(1979). The entire contents of both ESPY and WESTFELT are hereby
incorporated by reference as though set forth in full herein.
According to ESPY, a wet-strength resin should exhibit four key attributes.
These resins should first be water soluble, allowing for an even
dispersion and effective distribution over the cellulose fibers. Next, the
resins should have some cationic character, inherent or otherwise,
facilitating their adsorption onto anionic fibers in the pulp. The resins
should also be polymeric, with higher molecular weight polymers apparently
forming stronger bonds. Finally, the resins should be reactive, a quality
which allows them to be crosslinked to both themselves and to the
cellulose in the paper.
Resins comparable to those used for increasing paper strength also find
application in creping adhesives. In the manufacture of specific paper
products, such as facial tissue, bathroom tissue, or paper towels, the
paper web is subjected to a creping process in order to give the paper
product desirable characteristics, such as softness and bulk. Typically,
the creping process involves adhering the web, a cellulose web in the case
of paper, to a rotating creping cylinder, such as that used in a Yankee
dryer. The adhered web is then detached with a doctor blade. The impact of
the web against the blade disrupts fiber-to-fiber bonds within the web,
causing the web to wrinkle, or pucker.
The extent of creping action is dependent on several factors, including the
degree of adhesion between the web and the surface of the creping
cylinder. Greater adhesion between the web and cylinder results in
increased softness, albeit generally with some loss of strength. In order
to increase adhesion, a creping adhesive is often used. In addition,
creping adhesives can also reduce the wear on a dryer surface, provide
lubrication between a doctor blade and a dryer surface, reduce chemical
corrosion, and control the extent of creping. Ideally, a creping adhesive
adheres the sheet just tightly enough to the drum to produce a good crepe,
imparting absorbency and softness to the final product, with a minimal
loss of paper strength. However, if adhesion of the web to the dryer drum
is too strong, the sheet may pick or even "plug," i.e., underride the
doctor blade, and wrap around the dryer drum. On the other hand, if
adhesion is too weak, the sheet will lift off too easily and undergo too
little creping.
Examples of creping agents are disclosed in U.S. Pat. No. 5,187,219, to
FURMAN, U.S. Pat. No. 5,246,544, to HOLLENBERG et al., U.S. Pat. No.
5,338,807, to ESPY et al., and U.S. Pat. No. 5,374,334, to SOMNESE et al.
Other examples of creping agents are disclosed in U.S. Pat. Nos.
4,684,439, 4,788,243, 4,501,640, and 4,528,316, each to SOERENS. FURMAN,
HOLLENBERG et al., ESPY et al., SOMNESE et al., and SOERENS U.S. Pat. Nos.
'439, '243, '640, and '316, are hereby incorporated by reference as though
set forth in full herein.
The present invention advances the field of resin compositions for use in
paper making. Many of the resin compositions known in the art are toxic to
animals, or can be harmful to the environment. The present invention
provides an "environmentally friendly" alternative to the known additives
and resins. Embodiments of the present invention are essentially
chemically benign, using a biocatalytic process to induce crosslinking in
a paper product.
The use of a biocatalytic process to induce polymerization of phenols is
known in the art. DORDICK et al. describes the production of polymers
produced by horseradish peroxidase-catalyzed coupling of phenols in
"Polymerization of Phenols Catalyzed by Peroxidase in Nonaqueous Media,"
Biotechnology and Bioengineering Vol. 30, pgs. 31-36 (1987). POKORA et al.
describes the use of such catalytic processes in the production of
developer resins in U.S. Pat. No. 4,647,952 ('952), and expanded on those
processes in U.S. Pat. No. 4,900,671 ('671), and 5,153,298 ('298). POKORA
also describes the use of polyphenol resins in the production of paper in
U.S. Pat. No. 5,110,740 ('740). DORDICK et al. and POKORA et al. U.S. Pat.
Nos. '952, '671, '298, and '740, are hereby incorporated by reference as
though set forth in full herein.
The use of enzymes to catalyze the polymerization of phenols in monolayers
is described by AKKARA et al. in U.S. Pat. No. 5,143,828, and in
"Synthesis and Characterization of Polyphenols from Peroxidase-Catalyzed
Reactions," Enzyme Microb. Technol. vol. 13, page 521 (June 1991), as well
as in BRUNO et al., "Enzyme Catalyzed 2-D Polymerization of Phenol
Derivatives on a Langmuir-Blodgett Trough," Polymer Reprints, Vol. 32, No.
1, pgs. 232-233 (1991). The enzyme-catalyzed formation of polyesters is
described in U.S. Pat. No. 5,147,791, to MORROW et al. AKKARA et al.,
BRUNO et al., and MORROW et al., are hereby incorporated by reference as
though set forth in full herein.
The present invention provides novel and "environmentally friendly" methods
and resin and adhesive compositions. Such compositions are particularly
useful in the paper making process.
SUMMARY OF THE INVENTION
The present invention is directed to processes for producing adhesives and
resins, and to products made thereby.
The present invention is directed to processes for producing
oxidation-activated adhesives and resins, and to products made thereby.
The present invention is directed to producing enzyme-activated adhesives
and resins, and to the products made thereby.
The present invention is directed to methods for producing adhesive
compositions and resin compositions for use in making paper, and the
products made thereby.
The present invention is directed to methods of providing materials which
can be added at the wet end of paper production, increasing the strength
of a paper product.
The present invention is directed to producing articles which employ
activated adhesives and resins, including oxidation-activated adhesives
and resins.
The present invention is directed to methods of providing materials which
are chemically benign for addition at the wet end of paper production to
increase the strength of a paper product.
The present invention is directed to producing resins and adhesives, formed
from chemically benign materials, which can be used in paper making
processes.
The present invention is directed to producing a paper product which is
strengthened by a resin formed by the addition of chemically benign
materials at the wet end of production.
The present invention is directed to producing an adhesive for use in paper
creping.
The present invention is directed to producing a paper product which has
been formed through the use of such creping adhesive.
These and other aspects of the present invention are achieved by the
provision of a composition comprising (a) water-soluble polymeric material
comprising at least one nucleophilic polymer, (b) phenolic compound, and
(c) an oxidizing component.
In another manner of describing the present invention, there is provided a
composition comprising (a) water-soluble polymeric material comprising at
least one nucleophilic polymer, (b) phenolic compound, and (c) a component
capable of converting the phenolic compound into a quinone compound.
Component (c) may be a single component, or a mixture of components, and
preferably comprises the above-noted oxidizing component. For example, the
oxidizing component may comprise a member selected from the group
consisting of potassium dichromate, potassium permanganate, and mixtures
thereof or the oxidizing component may comprise a mixture of components
such as hydrogen peroxide and a material such as a metal catalyst, which
can cause hydrogen peroxide to release oxygen. Metal catalysts include,
but are not limited to, ferric chloride, cobalt chloride, cupric chloride,
and mixtures thereof.
Additionally, the oxidizing component may comprise an enzyme system. The
enzyme system may comprise at least one oxidation enzyme. For example, the
oxidation enzyme may comprise an oxidase, which preferably comprises a
member selected from the group consisting of laccase, tyrosinase,
polyphenol oxidase, and mixtures thereof. Alternatively, the oxidation
enzyme may comprise a peroxidase, which preferably comprises a member
selected from the group consisting of horseradish peroxidases, soybean
peroxidases, haloperoxidases, lactoperoxidases, bacterial peroxidases, and
mixtures thereof. More preferably, the peroxidase comprises horseradish
peroxidase.
When utilizing the enzyme system, the reaction can occur in the presence of
atmospheric air. However, the enzyme system preferably further comprises
at least one oxygen source. The oxygen source may comprise a member
selected from the group consisting of perborates, persulfates, peroxides,
and mixtures thereof. In alternative embodiments, the enzyme system may
comprise an alcohol oxidase and its corresponding alcohol, such as ethanol
and ethanol oxidase. Alternatively, the enzyme system may comprise a sugar
oxidase and its corresponding sugar, such as glucose and glucose oxidase
or galactose and galactose oxidase.
The oxidizing component may comprise an enzyme system in combination with
another oxidizing component, such as an enzyme system in combination with
potassium permanganate.
In preferred embodiments, the nucleophilic polymer comprises the following
general structure:
##STR1##
wherein n is an integer greater than 2, and R.sup.1 comprises a
hydrocarbyl group. Preferably the hydrocarbyl group comprises from about 2
to about 20 carbons. Preferably the hydrocarbyl group comprises from about
6 to about 10 carbons, and more preferably comprises about 6 carbons.
Preferably the hydrocarbyl group comprises an alkyl group having from
about 2 to about 20 carbons. Preferably the alkyl group comprises from
about 6 to about 10 carbons, and more preferably comprises about 6
carbons. In Formula I, preferably, n is from about 10 to about 200. More
preferably, n is from about 50 to about 100, and n is most preferably from
about 50 to about 80. The nucleophilic polymer may comprise a polyalkyl
amine or a polycyclic alkyl amine.
In alternative preferred embodiments, the nucleophilic polymer comprises
the following general structure:
##STR2##
wherein n is an integer greater than 2, X comprises a nucleophile, and Y
comprises a water solubility enabling group. In Formula II, the
nucleophile preferably comprises a member selected from the group
consisting of --NH.sub.2, --NHR.sup.2, --SH, --SOO.sup.-, --ArO.sup.-, and
--PR.sup.2.sub.2, wherein R.sup.2 comprises a hydrocarbyl group comprising
from about 1 to about 12 carbons, and Ar comprises a benzenoid, a
substituted benzenoid, or a napthalenoid group. Preferably the hydrocarbyl
group comprises a benzenoid group or an alkyl group comprising from about
1 to about 12 carbons. In Formula II, the water solubility enabling group
preferably comprises a cationic, an anionic, an amphoteric, or a hydrogen
bond participating group. In Formula II, the water solubility enabling
group preferably comprises a member selected from the group consisting of
--N.sup.+ (R.sup.3).sub.3, --COO.sup.-, --OSO.sub.3.sup.-,
--OPO.sub.3.sup.-, --N.sup.+ (R.sup.3).sub.2 --R.sup.3' --COO.sup.-, --OH,
--CONH.sub.2, and --B(OH).sub.2, wherein R.sup.3 and R.sup.3' each
comprise a hydrocarbyl group having from about 1 to about 12 carbons, such
as any straight chain or cyclic moiety.
The nucleophilic polymer may comprise a member selected from the group
consisting of polyvinyl alcohols, polyvinyl sulfones, polyacrylamides,
polyacrylates, polyacrylonitriles, polyethers, polyesters, polyarylethers,
polyarylsulfones, polyamides, polyimides, polyalkanes, polyaminoalkanes,
polyphenyls, and mixtures thereof.
The nucleophilic polymer may be formed by various processes, including a
process comprising at least one addition reaction followed by reduction.
Preferably, the nucleophilic polymer is formed by a reaction comprising a
member selected from the group consisting of nucleophilic displacement,
amination, nitration, sulfonation, phosphorylation, and combinations
thereof. The nucleophilic polymer may comprise a member selected from the
group consisting of --NH.sub.2, --NHR.sup.4, --SH, --SOO.sup.-,
--PR.sup.4.sub.2, --ArO.sup.-, and mixtures thereof, wherein R.sup.4
comprises a hydrocarbyl group comprising between about 1 and about 12
carbons, and Ar comprises a benzenoid or a napthalenoid group. Preferably
the hydrocarbyl group comprises a benzenoid group or an alkyl group
comprising from about 1 and about 12 carbons. The nucleophilic polymer may
be formed by polymerizing a monomer comprising a nucleophile. In preferred
embodiments, the nucleophilic polymer comprises polyvinyl amine alcohol,
which preferably comprises from about 0.01% to about 100% amine. More
preferably, the polyvinyl amine alcohol comprises from about 10% to about
50% amine, and most preferably, the polyvinyl amine alcohol comprises
about 12% amine.
The phenolic compound may comprise phenols or polyphenols. In preferred
embodiments, the phenolic material comprises the following general
chemical structure:
##STR3##
wherein Y comprises --H or --OH and X comprises --OR.sup.5, --R.sup.5,
--Ar, or --NR.sup.5 R.sup.5', wherein R.sup.5 and R.sup.5' comprise H or
a hydrocarbyl group comprising from about 1 to about 12 carbons, and Ar
comprises a benzenoid or napthalenoid group. Preferably the hydrocarbyl
group comprises an alkyl group comprising from about 1 to about 12
carbons. The phenolic compound may comprise a member selected from the
group consisting of polyphenols, substituted polyphenols, phenols,
substituted phenols, catechols, substituted catechols, hydroquinones,
substituted hydroquinones, aminophenols, substituted aminophenols, and
mixtures thereof. Preferably, the phenolic compound comprises
1,2-benzenediol. In alternative preferred embodiments, the phenolic
compound comprises 1,4-benzenediol.
The phenolic compound may comprise a polyphenolic compound, which
preferably comprises a member selected from the group consisting of
phloroglucinol, lignins, catechins, flavonoids, and mixtures thereof.
Preferably, such a polyphenolic compound is a naturally-occurring
compound. Alternatively, the polyphenolic compound may comprise a member
selected from the group consisting of polyphenols, resols, novolaks,
calixerenes, and mixtures thereof. Preferably, such a polyphenolic
compound is a synthetic compound.
In preferred embodiments, the compositions of the present invention may be
combined with a cellulosic material, which may comprise paper pulp.
These and other aspects of the present invention are further achieved by
the provision of a resin for imparting strength to a paper product,
produced by combining (a) water-soluble polymeric material comprising at
least one nucleophilic polymer, (b) phenolic compound, and (c) an
oxidizing component. Alternatively, component (c) may comprise a component
capable of converting the phenolic compound into a quinone compound. In
preferred embodiments, the oxidizing component may comprise an enzyme
system. This resin may be used in combination with cellulosic material,
such as fiber mat, woven cloth, box, board, sheet, wood, particle board,
wood stranded board, or laminate. These and other aspects of the present
invention are further achieved by the provision of a paper product
comprising such a resin.
These and other aspects of the present invention are further achieved by
the provision of a creping adhesive, produced by combining (a)
water-soluble polymeric material comprising at least one nucleophilic
polymer, (b) phenolic compound, and (c) an oxidizing component. In another
manner of describing the invention, component (c) may comprise a component
capable of converting the phenolic compound into a quinone compound. In
preferred embodiments, the oxidizing component comprises an enzyme system.
The creping adhesive may be used in combination with cellulosic material,
such as fiber mat, woven cloth, box, board, sheet, wood, particle board,
wood stranded board, or laminate. These and other aspects of the present
invention are further achieved by the provision of a paper product
comprising such creping adhesive.
These and other aspects of the present invention are further achieved by
the provision of a method of increasing the strength of a paper product,
comprising adding (a) water-soluble polymeric material comprising at least
one nucleophilic polymer, (b) phenolic compound, and (c) an oxidizing
component, to paper pulp. In another manner of describing the invention,
component (c) may comprise a component capable of converting the phenolic
compound into a quinone compound. In preferred embodiments, the oxidizing
component comprises an enzyme system.
These and other aspects of the present invention are further achieved by
the provision of a method of imparting strength to a cellulose-based
product comprising combining (a) water-soluble polymeric material
comprising at least one nucleophilic polymer, (b) phenolic compound, and
(c) an oxidizing component, to cellulosic starting materials. In another
manner of describing the invention, component (c) may comprise a component
capable of converting the phenolic compound into a quinone compound. In
preferred embodiments, the oxidizing component comprises an enzyme system.
These and other aspects of the invention are further achieved by the
provision of a kit comprising a water-soluble polymeric material
comprising at least one nucleophilic polymer, a phenolic compound, and a
component capable of converting the phenolic compound into a quinone
compound. In another manner of describing the invention, the component
capable of converting the phenolic compound into a quinone compound
comprises an oxidizing component. In some embodiments, the kit comprises
an oxygen source. In other embodiments, the kit does not include any
oxygen source.
DEFINITIONS
Certain terms and phrases are used repeatedly throughout the specification
and claims of this patent. The following definitions of these terms are
provided for consistency and clarity.
basis weight--the total weight of a sheet of paper of 3000 sf.
Canadian Standard of Freeness--a measure of the rate of drainage or the
pulp. Described in Pulp and Paper, Volume 1, James P. Casey, Interscience
Publishers, Inc., New York, 1952, page 341, the entire contents of which
volume is hereby incorporated by reference as though set forth in full
herein.
kraft--sulfate pulping method as described in Pulp and Paper, Volume 1,
James P. Casey, Interscience Publishers, Inc., New York, 1952, page 159.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
The present invention is directed to adhesives and resins usable in a
variety of applications.
In preferred embodiments, the present invention is directed to cross
linking systems for use as additives in the paper making process. In one
preferred embodiment, the present invention is directed to methods for
improving the creping process in paper production. In other preferred
embodiments, the present invention is further directed to methods for
improving the wet and dry strength of a paper product.
The present invention is not limited to uses in making paper. The present
invention is also applicable in the production of numerous cellulose-based
products, including fiber mat, woven cloth, box, board, sheet, wood,
particle board, wood stranded board, laminate, etc. Products such as these
are especially applicable to the present invention because they are
produced from cellulosic starting materials. In accordance with the
present invention, strength can be imparted to these products by the by
the addition of (a) water-soluble polymeric material comprising at least
one nucleophilic polymer, (b) phenolic compound, and (c) an oxidizing
component, to the cellulosic starting materials. In another manner of
describing the invention, component (c) may comprise a component capable
of converting the phenolic compound into a quinone compound.
Preferably, when used as an additive for improving paper strength, the
cross linking system of the present invention is added to the pulp at the
wet end of the process. The ingredients can also be added at the dry end
as a premix, or as separate ingredient streams. Preferably, when used as a
creping adhesive, the additives may be introduced at the wet end of the
process as well. Alternatively, it is also preferable to introduce a
resin, produced according to the present invention, directly onto the
creping cylinder prior to adhering the web to the drum. As a creping
adhesive, the material is preferably prepared as a premix, in which all
ingredients are mixed and allowed to develop into an adhesive constituent
prior to application to the creping cylinder.
Adhesives and resins of the present invention comprise: (a) water-soluble
polymeric material comprising at least one nucleophilic polymer, (b)
phenolic compound, and (c) an oxidizing component. In another manner of
describing the invention, component (c) may comprise a component capable
of converting the phenolic compound into a quinone compound.
When referring to components throughout this application, unless otherwise
noted, reference to a component in the singular also includes combinations
of the components. For example, as used herein, the term water-soluble
polymeric material comprising at least one nucleophilic polymer is meant
to include water-soluble polymers comprising nucleophiles, alone and/or in
combination. As used herein, the term phenolic compound is meant to
include phenolic compounds, alone and/or in combination. Further, as used
herein, an oxidizing component is meant to include oxidizing components,
alone and/or in combination.
As used herein, the term "hydrocarbyl" is understood to include
"aliphatic," "cycloaliphatic," and "aromatic." The hydrocarbyl groups are
understood to include alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl,
and alkaryl groups. Further, "hydrocarbyl" is understood to include both
non-substituted hydrocarbyl groups, and substituted hydrocarbyl groups,
with the latter referring to the hydrocarbon portion bearing additional
substituents, besides carbon and hydrogen.
In greater detail, the water-soluble polymer comprising a nucleophile may
be selected from any water-soluble polymer which comprises a nucleophile.
As used herein, the term water-soluble polymer refers to polymers which
can be made into a hot or cold aqueous solution at a concentration of at
least about 0.01%. Preferably, such polymer comprises polyalkyl amine,
polycyclic alkyl amine, polyvinyl alcohol, polyvinyl sulfone,
polyacrylamide, polyacrylate, polyacrylonitrile, polyether, polyester,
polyarylether, polyarylsulfone, polyamide, polyimide, polyalkane,
polyaminoalkane, and/or polyphenyl. Most preferably, the polymer comprises
polyvinyl amine alcohol. Preferably, the polyvinyl amine alcohol comprises
from about 0.01% to about 100% amine; more preferably comprises from about
10% to about 50% amine; and most preferably comprises about 12% amine.
The nucleophile may be any known nucleophile, and preferably comprises
--NH.sub.2, --NHR.sup.4, --SH, --SOO.sup.-, --PR.sup.4.sub.2, and
--ArO.sup.-, or mixtures thereof, wherein R.sup.4 comprises a hydrocarbyl
group in which the number of carbons ranges from about 1 to about 12, and
Ar comprises a benzenoid or napthalenoid group. Preferably the hydrocarbyl
group comprises a benzenoid group or an alkyl group comprising from about
1 to about 12 carbons. The nucleophile may be attached to the polymer
backbone in any manner known in the art. Preferably, the nucleophile is
attached by a process comprising an addition reaction, followed by
reduction. Preferably, the nucleophile is attached via nucleophilic
displacement, amination, nitration, sulfonation, phosphorylation, or
combinations thereof, each followed by reduction. In other preferable
embodiments, the nucleophile is part of the monomer which polymerizes to
form the polymer.
The following formula is a schematic structural representation of the
general chemical formula of the water-soluble polymer of one embodiment of
the invention, wherein the nucleophile is part of the polymer backbone:
##STR4##
In Formula I, the brackets are meant to illustrate that the depicted
portion is repeated n number of times. In Formula I, n may be any integer
greater than 2, and is preferably between 10 and 200. More preferably, in
Formula I, n is between 50 and 100, and n is most preferably between 50
and 80. In Formula I, R.sup.1 may be any hydrocarbyl group. Preferably,
the hydrocarbyl group comprises from about 2 to about 20 carbons. More
preferably, the hydrocarbyl group comprises from about 6 to about 10
carbons, and most preferably comprises about 6 carbons. Preferably the
hydrocarbyl group comprises an alkyl group having from about 2 to about 20
carbons. More preferably, the alkyl group has from about 6 to about 10
carbons. Most preferably, in Formula I, the alkyl group comprises 6
carbons. Examples of polymers which exhibit this general structure
include, but are not limited to, polyalkyl amine, and polycyclic alkyl
amine.
The following formula is a schematic chemical representation of the general
chemical formula of a water-soluble polymer of one embodiment of the
invention, wherein the nucleophile is attached to the polymer backbone:
##STR5##
In Formula II, the brackets are meant to illustrate that the depicted
portion is repeated n number of times. In Formula II, n may be any integer
greater than 2, and is preferably greater than 100. In Formula II, X
comprises any nucleophile, and preferably comprises --NH.sub.2,
--NHR.sup.2, --SH, --SOO.sup.-, --PR.sup.2.sub.2, and ArO.sup.-, wherein
R.sup.2 comprises a hydrocarbyl group having from about 1 to about 12
carbons, and Ar comprises a benzenoid or substituted benzenoid, or a
napthalenoid group. Preferably the hydrocarbyl group comprises a benzenoid
group or an alkyl group having from about 1 to about 12 carbons. In
Formula II, Y comprises any water solubility enabling group, and is
preferably a cationic, an anionic, an amphoteric, or a hydrogen bond
participating group, such as --N.sup.+ (R.sup.3).sub.3 (where R.sup.3 is
any moiety having from about 1 to about 12 carbons, such as a C1-C12
straight chain or C1-C12 cyclic moiety), --COO.sup.-, --OSO.sub.3.sup.-,
--OPO.sub.3.sup.-, --N.sup.+ (R.sup.3).sub.2 --R.sup.3' --COO.sup.-
(where R.sup.3 and R.sup.3' are any moiety having from about 1 to about
12 carbons, such as any C1-C12 straight chain or C1-C12 cyclic moiety),
--OH, --CONH.sub.2, and --B(OH).sub.2.
Examples of polymers in which the nucleophile is attached to the polymer
backbone include, but are not limited to, polyvinyl alcohols, polyvinyl
sulfones, polyacrylamides, polyacrylates, polyacrylonitriles, polyethers,
polyesters, polyarylethers, polyarylsulfones, polyamides, polyimides,
polyalkanes, polyaminoalkanes, polyphenyls, and mixtures thereof.
The phenolic compound for use in the invention may comprise polyphenols,
substituted polyphenols, phenols, substituted phenols, catechols,
substituted catechols, hydroquinones, substituted hydroquinones,
aminophenols, substituted aminophenols, and/or mixtures thereof. The
following formula schematically depicts the general chemical structure of
a preferred phenolic compound according to the invention:
##STR6##
In Formula III, X preferably comprises --OR.sup.3, --R.sup.3, --NR.sup.3
R.sup.3', or --Ar, wherein R.sup.3 and R.sup.3' comprise H or a
hydrocarbyl group comprising from about 1 to about 12 carbons, and Ar
comprises a benzenoid or napthalenoid group. Preferably the hydrocarbyl
group comprises an alkyl group having from about 1 to about 12 carbons. In
Formula III, Y preferably comprises --OH or --H. Examples of phenolic
compounds which exhibit this general structure include, but are not
limited to, phenol, catechol, hydroquinone, and aminophenol. Most
preferably, the phenolic material comprises 1,2-benzenediol and/or
1,4-benzenediol. In other preferred embodiments, the phenolic compound may
comprise a polyphenolic compound which may be of natural or synthetic
origin. Preferable natural polyphenolic compounds include, but are not
limited to, phloroglucinol, lignin, catechins, flavonoids, and mixtures
thereof. Preferable synthetic polyphenolic compounds include, but are not
limited to, polyphenol, resol, novolak, calixerenes, and mixtures thereof.
The present invention includes a component capable of converting the
phenolic compound into a quinone compound. In another manner of describing
the invention, this component may be an oxidizing component. The oxidizing
component may comprise potassium dichromate, potassium permanganate, or
mixtures thereof. The oxidizing component may comprise mixtures such as
hydrogen peroxide and a material such as a metal catalyst which is capable
of causing hydrogen peroxide to release oxygen. Metal catalysts include,
but are not limited to, ferric chloride, cobalt chloride, cupric chloride,
and mixtures thereof.
The oxidizing component preferably comprises an enzyme system. The enzyme
system preferably comprises at least one oxidative enzyme component. In
preferable embodiments, the enzyme component may comprise an enzyme such
as an oxidase or peroxidase. Preferable oxidases and peroxidases include,
but are not limited to, laccases, tyrosinases, polyphenol oxidases,
horseradish peroxidases, soybean peroxidases, haloperoxidases,
lactoperoxidases, bacterial peroxidase, and combinations thereof. Other
preferable embodiments comprise combinations of different oxidases,
combinations of different peroxidases, or combinations of oxidases and
peroxidases. Most preferably, the enzyme component comprises horseradish
peroxidase.
When utilizing the enzyme system, the reaction can occur in the presence of
atmospheric air. However, the enzyme system preferably further comprises
at least one oxygen source. The oxygen source may be direct, in which the
oxygen is present as elemental oxygen, and/or indirect, in which the
oxygen is released from a more complex molecule. Preferably the oxygen
source comprises a source such as perborates, persulfates, peroxides, and
mixtures thereof.
Other preferable enzyme systems comprise a mixture of a sugar oxidase and
the corresponding sugar, such as galactose oxidase and galactose or
glucose oxidase and glucose. Other preferable enzyme systems comprise an
alcohol oxidase and the corresponding alcohol, such as ethanol oxidase and
ethanol. Preferably, the enzyme system comprises horseradish peroxidase
and the reaction occurs in the presence of atmospheric air.
Without being bound by theory, it is believed that, in the presence of an
oxidizing component, a phenolic compound is made reactive by conversion
into a quinone compound. In the presence of a substrate and a polymeric
compound which comprises a nucleophilic moiety, the activated phenolic
compound reacts with the polymer and the substrate to form a crosslink.
The following reaction, Reaction I, is a schematic chemical representation
of the aforementioned reaction as it might occur:
##STR7##
Without further elaboration, it is believed that one skilled in the art
can, using the preceding description, utilize the present invention to its
fullest extent. The following preferred specific embodiments are,
therefore, to be construed as merely illustrative, and not limitative of
the remainder of the disclosure in any way whatsoever.
The entire disclosures of all patents and publications, cited above and
below, are hereby incorporated by reference as though set forth in full
herein.
EXAMPLES
Examples 1-6
Enzyme Activated Polymer System Imparts Strength to Paper
Handsheets are made on a Noble and Wood Sheet Machine (Noble and Wood
Machine Co., Hoosick Falls, N.Y.) using standard hard water at a
controlled pH. Standard hard water (50 ppm alkalinity and 100 ppm
hardness) is made by mixing deionized water with CaCl.sub.2 and
NaHCO.sub.3. Control of pH is achieved by using NaOH or H.sub.2 SO.sub.4.
The pulp is beaten to the desired freeness at a consistency of 2.5 weight
%. The beaten pulp is added to a proportioner at a controlled level
(depending on final desired basis weight). For 80 lb/3000 ft.sup.2 basis
weight, 4000 ml of beaten pulp is used. For 40 lb/3000 ft.sup.2 basis
weight, 2000 ml of beaten pulp is used. The beaten pulp is diluted to 18
liters with standard hard water. Chemical additions and pH adjustments are
made to the proportioner as desired, with continuous mixing.
A clean and wetted 100 mesh screen is placed on an open deckle box, which
is then closed. Standard hard water and 920 ml of pulp mixture from the
proportioner are then added to the deckle box, and couched. Ingredients in
accordance with the present invention are added to the deckle box, and
mixed. The water is then drained from the box, and the sheet removed. The
sheet is wet pressed between felts with press weights adjusted to give a
solids content of 33-34%. The sheet and screen are then placed on a drum
dryer, which is adjusted to a temperature of approximately 228-232.degree.
F. and throughput time of 50-100 seconds, depending on basis weight. Final
sheet moisture content is 3-5%. A single sheet is made from 920 ml of the
pulp mixture. Five sheets minimum are tested for each experimental set.
Tensile testing is done on the handsheets according to TAPPI Method T 494
om-88 ("TAPPI Test Methods," TAPPI Press, Atlanta, Ga., 1996).
For EXAMPLES 1-6, the following materials are added in accordance with the
invention: polyvinyl amine alcohol, molecular weight of approximately 100
Kd, 6% amine (Air Product); catechol, 99% pure (Aldrich Chemical);
hydroquinone (Eastman Kodak Chemical); peroxidase (Sigma Chemical);
hydrogen peroxide, 3% solution (Baker Chemical). The specific amounts
which are added to each batch (920 ml pulp mixture) are disclosed in Table
1. Additives are added as solutions in 10 ml water. For EXAMPLES 1-6,
paper is manufactured at 80 lbs basis weight: 920 ml pulp mixture yielded
5.1 g pulp (weight of paper). Unless otherwise specified, the ratios shown
in the Table are weight/weight. The following abbreviations are used in
Table 1: polyvinyl amine alcohol, PVAA; catechol, CAT; hydroquinone, HQ;
peroxidase, PER; and hydrogen peroxide, H.sub.2 O.sub.2. Blank indicates
no additional chemicals are added.
TABLE 1
______________________________________
EFFECT ON PAPER STRENGTH
WET DRY
TENSILE TENSILE
EXAMPLE DESCRIPTION (lbs/in) (lbs/in)
______________________________________
1 BLANK 1.6 44.7
2 51 mg PVAA 8.8 59.3
(MW 100K, 6% amine)
3 51 mg PVAA/5.1 mg CAT
8.8 49.9
(10/1)
4 51 mg PVAA/5.1 mg CAT/
9.9 58.1
0.25 mg PER (10/1/0.05)
5 51 mg PVAA/5.1 mg CAT/
9.8 56.6
0.25 mg PER/1.25 mg H.sub.2 O.sub.2
(10/1/0.05/0.25)
6 51 mg PVAA/5.1 mg HQ/
12.6 74.5
0.25 mg PER (10/1/0.05)
______________________________________
Examples 1-6 are presented as evidence that embodiments of the present
invention impart strength to a paper product. The results presented in
Table 1 clearly demonstrate the substantial increases in paper strength
imparted by the present invention.
Examples 7-12
Effect of the Molecular Weight of the Polymer on Paper Strength
The paper is made according to the procedures set forth in EXAMPLES 1-6
above, with the exception that different amounts and kinds of materials
were added, according to the invention. The specific amounts which are
added to each batch (920 ml pulp mixture per piece of paper) are disclosed
in Table 2. Additives are added as solutions in 10 ml water. Paper is
manufactured at 80 lbs basis weight: 920 ml pulp mixture yielded 5.1 g
pulp (weight of paper). The following new abbreviations are introduced for
use in Table 2: polyvinyl amine alcohol (MW approximately 100 Kd, 6%
amine), PVAA1; polyvinyl amine alcohol (MW approximately 30 Kd, 12%
amine), PVAA2.
TABLE 2
______________________________________
EFFECT OF THE MOLECULAR WEIGHT OF THE POLYMER
WET DRY
TENSILE TENSILE
EXAMPLE DESCRIPTION (lbs/in) (lbs/in)
______________________________________
7 BLANK 1.8 48.3
8 51 mg PVAA1 13.2 63.9
9 51 mg PVAA2 9.8 59.7
10 51 mg PVAA1/ 16.7 78.2
5.1 mg CAT/
1.25 mg PER (10/1/0.25)
11 51 mg PVAA2/ 10.8 63.5
5.1 mg CAT/
1.25 PER (10/1/0.25)
12 51 mg PVAA2/ 14.8 68.2
5.1 mg HQ/
1.25 mg PER (10/1/0.25)
______________________________________
Because the molecular weight of the polymer used in the present invention
can have an effect on the strength imparted to the paper product, EXAMPLES
7-12 are provided to demonstrate this effect. Two different molecular
weights of polymer were tested, 100 Kd and 30 Kd. From the results
presented in Table 2, it is clear that the 100 Kd polymer performs better
than the 30 Kd polymer.
Examples 13-18
Effect of the pH of the Paper Making Conditions
The paper is made according to the procedure set forth in EXAMPLES 1-6
above, with the exception that different amounts and kinds of materials
were added, according to the invention, and the basis weight for the paper
is 40 lbs. The weight per piece of paper is 2.5 g. The amounts and kinds
of materials specifically used are disclosed in Table 3.
TABLE 3
______________________________________
EFFECT OF THE PH OF THE PAPER MAKING CONDITIONS
WET DRY
TENSILE TENSILE
EXAMPLE pH DESCRIPTION (lbs/in)
(lbs/in)
______________________________________
13 7.5 BLANK 0.7 20.2
14 7.5 25 mg PVAA 5.3 27.4
(MW 100k, 6% amine)
15 7.5 25 mg PVAA/ 5.4 28.8
0.6 mg PER (10/0.25)
16 7.5 25 mg PVAA/ 7.3 36.7
2.5 mg CAT/
0.6 mg PER (10/1/0.25)
17 5.5 25 mg PVAA/ 4.9 29.1
0.6 mg PER (10/0.25)
18 5.5 25 mg PVAA/ 7.0 34.5
2.5 mg CAT/
0.6 mg PER (10/1/0.25)
______________________________________
Because the pH of an enzymatic reaction can have an effect on the reaction
itself, Examples 13-18 are provided to demonstrate this effect. The
results presented in Table 3 demonstrate that the reaction according to
the present invention performs slightly better at pH 7.5 than at pH 5.5.
Examples 19-23
Effect of Phenol and Diamine Compounds on Paper Strength
The paper is made according to the procedure set forth in EXAMPLES 1-6
above, with the exception that different amounts and kinds of materials
are added, according to the invention. The amounts and kinds of materials
which are specifically used are disclosed in Table 4. The following new
abbreviations are introduced for use in Table 4: ethylene diamine, MW
approximately 600, ED-600; ethylene diamine, MW approximately 2000,
ED-2001; phenol, PHE; hydrogen peroxide, H.sub.2 O.sub.2.
TABLE 4
______________________________________
EFFECT OF PHENOL AND DIAMINE COMPOUNDS
WET DRY
EX- STRENGTH STRENGTH
AMPLE DESCRIPTION (lbs/in) (lbs/in)
______________________________________
19 BLANK 1.7 51.0
20 51 mg PVAA/ 11.5 61.5
2.8 mg CAT/
0.51 mg PER (10/0.56/0.1)
21 51 mg PVAA/2.8 mg PHE/
13.0 65.1
0.7 mg PER/0.7 mg H.sub.2 O.sub.2
(10/0.56/0.14/0.14)
22 51 mg PVAA/15 mg ED-600/
11.6 60.0
5.5 mg CAT/1.4 mg PER
(10/3/1.07/0.27)
23 51 mg PVAA/15 mg ED-2001/
11.9 57.9
5.5 mg CAT/1.4 mg PER
(10/3/1.07/0.27)
______________________________________
These examples are presented to show that one can blend in diamine
compounds into the formulation with success.
From the foregoing descriptions, one skilled in the art can easily
ascertain the essential characteristics of this invention, and without
departing from the spirit and scope thereof, can make various changes and
modifications of the invention to adapt it to various usages and
conditions.
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